CN102344517B - Polymer microballoons and preparation method thereof - Google Patents
Polymer microballoons and preparation method thereof Download PDFInfo
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- CN102344517B CN102344517B CN201110190804.9A CN201110190804A CN102344517B CN 102344517 B CN102344517 B CN 102344517B CN 201110190804 A CN201110190804 A CN 201110190804A CN 102344517 B CN102344517 B CN 102344517B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 38
- 239000012530 fluid Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000012071 phase Substances 0.000 claims description 68
- 238000003756 stirring Methods 0.000 claims description 43
- 238000003860 storage Methods 0.000 claims description 36
- 239000011324 bead Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 31
- 239000006185 dispersion Substances 0.000 claims description 24
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- 238000010557 suspension polymerization reaction Methods 0.000 claims description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 19
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 18
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 229960005419 nitrogen Drugs 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 230000002209 hydrophobic effect Effects 0.000 abstract 1
- 238000010558 suspension polymerization method Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 239000000375 suspending agent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 239000004794 expanded polystyrene Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
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- 230000035484 reaction time Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- NMFLQJPYTHAGCO-UHFFFAOYSA-N diethyl 3-phenylbenzene-1,2-dicarboxylate Chemical compound CCOC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(=O)OCC NMFLQJPYTHAGCO-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
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- 239000002609 medium Substances 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
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- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses polymer microballoons and a preparation method thereof. The preparation method comprises the following steps of mixing well one or more hydrophobic alkene monomers and an oil-soluble initiator to obtain oil phase fluid dispersed uniformly, crushing and dispersing the oil phase fluid into oil drops having even sizes by a jet-flow suspension polymerization method, wherein the oil drops form uniform O/W suspension in a water phase, and carrying out constant-temperature polymerization to obtain the polymer microballoons having even sizes. The polymer microballoons prepared by the preparation method have the advantages of even microballoon size, controllable size, controllable aperture size, stable chemical property, and potential application value in food safety detection and biotechnological drug separation.
Description
Technical field
The present invention relates to polymer bead and preparation method thereof, particularly a kind of monodisperse polymer microballon and preparation method thereof.
Background technology
In recent years, polymer bead shows unique advantage in bioseparation engineering and field of detection of food safety, having tempting application prospect in the Application Areas such as separation, immobilized enzyme, food safety detection of proteins and peptides especially, is one of hot subject of current research development & application.
The method of prior art synthetic polymer microballon mainly contains suspension polymerization, dispersion copolymerization method and seed swelling polymerization method.
Suspension polymerization due to preparation technology simple, cost is low, is the most blanket method of current synthetic polymer microballon.The method be by the monomer that is dissolved with initiator under the effect of violent stirring and dispersion agent, be suspended in the polymerisation process carried out in water with droplet-like.The system composition of suspension polymerization mainly comprises slightly water-soluble monomer, oil-soluble initiator, water and dispersion agent four basal component.Polyreaction is carried out in monomer droplet, from single monomer droplet, its composition and polymerization mechanism identical with mass polymerization, be therefore also called globule mass polymerization.The advantage of suspension polymerization is owing to having water as dispersion medium, and thus heat conduction is easy, and polymer reaction is easy to control, and product is easily separated.But the method adopts the dispersion of mechanical stirring slurry, due to can shearing force be produced when stirring rake stirs in a kettle., each several part drop discontinuity in reactor, cause monomer droplet not of uniform size, the polymer bead particle diameter of final synthesis is large, distribution of sizes is wide, thus have impact on its result of use.
Dispersion copolymerization method is first proposed by the investigators of ICI company of Britain early 1970s, compare with other polymerization processs, dispersion copolymerization method production technique is simple, reasonably can solve heat dissipation problem, be applicable to various monomer, and the monodisperse polymer microballoon of different-grain diameter rank can be prepared.
The standby polymer bead of seed swelling polymerization legal system is more even, but adopt a large amount of organic solvents to carry out multi-step swelling, not only to environment, and need the longer reaction times (usually needing 3-7 days) that a collection of polymer bead could be synthesized, therefore its production cost is very high.
For suspension polymerization, study more.It is mostly lipophilicity vinyl monomer and oil-soluble initiator composition oil phase be dispersed in aqueous phase, high speed machine stir and stablizer effect under, oil phase is that drop state is dispersed in aqueous phase, add thermal-initiated polymerization formation polymer bead.
Such as CN 1803857A discloses a kind of method of synthesizing micron grade polymer microsphere by suspension polymerization, and the method adopts glucose/water to be medium system, and stablizer is polyvinyl alcohol, suspension polymerization synthesizing monodisperse micron-level crosslinked polystyrene microsphere; Polymerizing condition is glucose/water is 5 ~ 10% (wt%), vinylbenzene 20 ~ 30% (wt%), divinylbenzene 0.3 ~ 1% (wt%), Diisopropyl azodicarboxylate 0.5 ~ 1.5% (wt%), polyvinyl alcohol 2 ~ 4.5% (wt%), temperature of reaction 70 ~ 85 degrees Celsius, 9 ~ 14 hours reaction times, reaction atmosphere N
2, the crosslinked polystyrene microsphere particle diameter prepared with this understanding is between 10 ~ 20nm, and dispersion coefficient is between 0.020 ~ 0.046.
CN 102030849 A discloses a kind of pearl suspension polymerization of methyl methacrylate, comprises and makes oil phase and aqueous phase mix and carry out the step of suspension polymerization.Described oil phase comprises methyl methacrylate monomer and oleosoluble radical initiators; Described aqueous phase comprises water and at least three kinds of suspension agents.In these three kinds of suspension agents, a kind of suspension agent is cellulose family tensio-active agent; A kind of suspension agent is vinylpyrrolidinone polymer nonionic surface active agent; A kind of suspension agent is acrylic polymers anion surfactant.
Aforesaid method due in reaction process the dispersion effect of drop poor, the size distribution of the polymer bead therefore synthesized is very wide.By improvement suspension polymerization dispersing apparatus, such as, in reactor, install spiral stirrer additional, the performance of polymer bead can be improved to a certain extent.
CN 200974014Y discloses a kind of agitation equipment of polymerization vessel for micro-paste resin that suspends, the agitator mechanomotive force that it comprises with motor, wheel box and output shaft exports total journey, agitator, the inner side output shaft that this agitator is included in the total journey of Power output being connected with one is connected with the pipe core of cooling circulating water, and the inner side be connected with pipe core is connected with the screw mixing oar of cooling circulating water.By installing helical stir additional in former still, can precession polymeric kettle, the stirring making diameter larger can be pacified into less polymeric kettle suitable for reading, in auxiliary stirring rake, pass into water coolant, increases heat transfer area, improves cooling performance.
Even if but by above-mentioned improvement, the microballon size that described method prepares still very heterogeneity.Therefore, the preparation method inquiring into a kind of monodisperse polymer microballon is key issue to be solved.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of method adopting jet flow suspension polymerization to prepare monodisperse polymer microballon.Described method overcomes typical polymerization reaction can not synthesize the defect that homogeneous polymer bead and prepared polymer bead thereof exist in performance.
The preparation method of a kind of polymer bead of the present invention, comprises the following steps:
(1) hydrophobicity vinyl monomer is mixed with oil-soluble initiator, fully stir, form homodisperse oil phase fluid; Described mixing and stirring preferably complete in oil phase storage tank;
(2) in stirring-type polymerization reaction kettle, add stablizer and water, dispersed with stirring forms uniform aqueous phase solution;
(3) add suitable pressure, described oil phase fluid is entered in described aqueous phase solution by nozzle dispersion and forms uniform O/W type suspension;
(4) constant temperature polyreaction, can obtain the polymer bead of uniform particle diameter.
Two of object of the present invention is the preparation method's special purpose device providing a kind of described polymer bead, described device is jet flow suspension polymerization device, described jet flow suspension polymerization device comprises polymerization reaction kettle, oil phase storage tank and nozzle, oil phase storage tank upper end first variable valve is connected with nitrogengas cylinder, and is connected through the nozzle of the second variable valve with polymerization reaction kettle upper end; Oil phase storage tank upper end is provided with tensimeter and motor, and driven by motor agitator rotates.
Three of object of the present invention is to provide a kind of polymer bead, and described polymer bead is prepared by foregoing method.Compared to the polymer bead that existing suspension polymerization prepares, method of the present invention imparts the new characteristic of polymer bead, its uniform particle diameter, and size is adjustable, and this is that existing suspension polymerization cannot prepare.
As preferably, the preparation method of polymer bead of the present invention, comprises the following steps:
(1) jet flow suspension polymerization device is prepared:
Described jet flow suspension polymerization device comprises polymerization reaction kettle, oil phase storage tank and nozzle, and oil phase storage tank upper end first variable valve is connected with nitrogengas cylinder, and is connected through the nozzle of the second variable valve with polymerization reaction kettle upper end; Oil phase storage tank upper end is provided with tensimeter and motor, and driven by motor agitator rotates;
(2) hydrophobicity vinyl monomer is mixed with oil-soluble initiator, fully stir, in oil phase storage tank, form homodisperse oil phase fluid;
(3) in stirring-type polymerization reaction kettle, add stablizer and water, dispersed with stirring forms uniform aqueous phase solution;
(4) add suitable pressure, the oil phase fluid in oil phase storage tank is entered in aqueous phase by nozzle dispersion and forms uniform O/W type suspension;
(5) constant temperature polyreaction, can obtain the polymer bead of uniform particle diameter.
Those skilled in the art are as can be seen from technique scheme, and polymer bead preparation method of the present invention, can substitute the suspension polymerization of prior art, and it may be used for the preparation of any suitable polymer bead.
As optimal technical scheme, the present invention preferably but be not limited to following restriction:
Described hydrophobicity vinyl monomer is preferably made up of one or more hydrophobicity vinyl monomer; Described hydrophobicity vinyl monomer is preferably vinylbenzene, divinylbenzene, methyl methacrylate, methyl acrylate, vinyl acetate, glycidyl methacrylate or derivatives thereof.
Described oil-soluble initiator is preferably benzoyl peroxide.
Described stablizer is one or more tensio-active agent, and described tensio-active agent is preferably polyvinyl alcohol, polyvinylpyrrolidone, Mierocrystalline cellulose, HPMC or its mixture.
The temperature of described polyreaction is preferably 70 ~ 90 DEG C, is more preferably 80 DEG C.
The preparation method of a kind of polymer bead provided by the invention, adopts jet flow dispersion to substitute mechanical stirring dispersion, the dispersion of oil phase fluid well-distributing and polyreaction is separately carried out.By injection, oil phase fluid well-distributing is broken and in aqueous phase, form stable O/W type suspension, polyreaction can obtain the polymer bead of uniform particle diameter.
The advantage of the preparation method of a kind of polymer bead provided by the invention is as follows:
(1) the polymer bead uniform particle diameter prepared, size is adjustable;
(2) aperture of the polymer bead prepared is adjustable;
(3) the polymer bead chemical stability prepared is good;
(4) simple, the low price of preparation technology;
(5) easily expanding production is carried out.
Embodiment
Embodiment one
(1) by the organic phase that 80g vinylbenzene, 10g divinylbenzene and 3g benzoyl peroxide form, adding in oil phase storage tank, forming uniform oil phase fluid through stirring;
(2) in stirring-type polymerization reaction kettle, add 1000ml distilled water and 10g polyvinyl alcohol, after 80 DEG C of constant temperature stir 30min, polyvinyl alcohol is dissolved completely, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in oil phase storage tank keep 0.1MPa, open the second variable valve, oil phase fluid is entered in polymerization reaction kettle by nozzle dispersion and forms O/W suspension in aqueous phase, constant temperature 80 DEG C reaction 3h;
(4), after cooling, through operations such as centrifugation, washing, oven dry, ganoid polystyrene microbeads can be obtained.
Embodiment two
(1), by the organic phase that 70g methyl methacrylate, 5g Ethylene glycol dimethacrylate and 4g benzoyl peroxide form, in impouring oil phase storage tank, uniform oil phase fluid is formed through stirring;
(2) in stirring-type polymerization reaction kettle, add 1000ml distilled water and 15g polyvinylpyrrolidone, after 80 DEG C of constant temperature stir 30min, polyvinylpyrrolidone is dissolved completely, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in oil phase storage tank keep 0.1MPa, open the second variable valve, oil phase fluid is entered in polymerization reaction kettle by nozzle dispersion and forms O/W suspension in aqueous phase, constant temperature 80 DEG C reaction 3h;
(4), after cooling, through operations such as centrifugation, washing, oven dry, polymethylmethacrylate microballon can be obtained.
Embodiment three
(1) organic phase of 70g vinyl acetate, 4g divinylbenzene and 4g benzoyl peroxide composition, adds in oil phase storage tank, forms uniform oil phase fluid through stirring;
(2) in stirring-type polymerization reaction kettle, add 1000ml distilled water and 15g polyvinyl alcohol, after 80 DEG C of constant temperature stir 30min, polyvinyl alcohol is dissolved completely, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in oil phase storage tank keep 0.1MPa, open the second variable valve, oil phase fluid is entered in polymerization reaction kettle by nozzle dispersion and forms O/W suspension in aqueous phase, constant temperature 80 DEG C reaction 3h;
(4), after cooling, through operations such as centrifugation, washing, oven dry, ganoid polyvinyl acetate (PVA) microballon can be obtained.
Embodiment four
(1) organic phase of 70g methyl acrylate, 4g divinylbenzene and 4g benzoyl peroxide composition, adds in oil phase storage tank, forms uniform oil phase fluid through stirring;
(2) in stirring-type polymerization reaction kettle, add 1000ml distilled water and 15g polyvinyl alcohol, after 80 DEG C of constant temperature stir 30min, polyvinyl alcohol is dissolved completely, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in oil phase storage tank keep 0.1MPa, open the second variable valve, oil phase fluid is entered in polymerization reaction kettle by nozzle dispersion and forms O/W suspension in aqueous phase, constant temperature 80 DEG C reaction 3h;
(4), after cooling, through operations such as centrifugation, washing, oven dry, ganoid polymethyl acrylate microballon can be obtained.
Embodiment five
(1) organic phase of 80g glycidyl methacrylate, 4g Ethylene glycol dimethacrylate and 3g benzoyl peroxide composition, adds in oil phase storage tank, forms uniform oil phase fluid through stirring;
(2) in stirring-type polymerization reaction kettle, add 1000ml distilled water and 20g polyvinyl alcohol, after 80 DEG C of constant temperature stir 30min, polyvinyl alcohol is dissolved completely, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in oil phase storage tank keep 0.1MPa, open the second variable valve, oil phase fluid is entered in polymerization reaction kettle by nozzle dispersion and forms O/W suspension in aqueous phase, constant temperature 80 DEG C reaction 3h;
(4), after cooling, through operations such as centrifugation, washing, oven dry, ganoid poly (glycidyl methacrylate) microballon can be obtained.
Embodiment six
(1) by the organic phase that 80g vinylbenzene, 10g divinylbenzene, 30g methyl isobutyl carbinol and 3g benzoyl peroxide form, adding in oil phase storage tank, forming uniform oil phase fluid through stirring;
(2) in stirring-type polymerization reaction kettle, add 1000ml distilled water and 20g polyvinyl alcohol, after 80 DEG C of constant temperature stir 30min, polyvinyl alcohol is dissolved completely, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in oil phase storage tank keep 0.1MPa, open the second variable valve, oil phase fluid is entered in polymerization reaction kettle by nozzle dispersion and forms O/W suspension in aqueous phase, constant temperature 80 DEG C reaction 3h;
(4) be cooled to room temperature, filtered polymeric microballon, by water, acetone, washing with alcohol, to remove pore-creating agent, expanded polystyrene microballon can be obtained.
Embodiment seven
(1) by the organic phase that 80g vinylbenzene, 10g divinylbenzene, 20g dimethylbenzene and 3g benzoyl peroxide form, adding in oil phase storage tank, forming uniform oil phase fluid through stirring;
(2) in stirring-type polymerization reaction kettle, add 1000ml distilled water, 10g polyvinyl alcohol and 10g polyvinylpyrrolidone, after 80 DEG C of constant temperature stir 30min, polyvinyl alcohol is dissolved completely, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in oil phase storage tank keep 0.1MPa, open the second variable valve, oil phase fluid is entered in polymerization reaction kettle by nozzle dispersion and forms O/W suspension in aqueous phase, constant temperature 80 DEG C reaction 3h;
(4) be cooled to room temperature, filtered polymeric microballon, by water, acetone, washing with alcohol, to remove pore-creating agent, expanded polystyrene microballon can be obtained.
Embodiment eight
(1) organic phase of 80g glycidyl methacrylate, 10g Ethylene glycol dimethacrylate, 40g biphenyl dicarboxylic acid diethyl ester and 3g benzoyl peroxide composition, adds in oil phase storage tank, forms uniform oil phase fluid through stirring;
(2) in stirring-type polymerization reaction kettle, add 1000ml distilled water and 5g HPMC, after 80 DEG C of constant temperature stir 30min, polyvinyl alcohol is dissolved completely, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in oil phase storage tank keep 0.1MPa, open the second variable valve, oil phase fluid is entered in polymerization reaction kettle by nozzle dispersion and forms O/W suspension in aqueous phase, constant temperature 80 DEG C reaction 3h;
(4) be cooled to room temperature, filtered polymeric microballon, by water, acetone, washing with alcohol, to remove pore-creating agent, porous polymethyl glycidyl acrylate microballon can be obtained.
Embodiment nine
(1) by the organic phase that 80g vinylbenzene, 10g divinylbenzene, 10g dimethylbenzene, 10g methyl isobutyl carbinol and 3g benzoyl peroxide form, adding in oil phase storage tank, forming uniform oil phase fluid through stirring;
(2) in stirring-type polymerization reaction kettle, add 1000ml distilled water, 10g polyvinyl alcohol and 10g polyvinylpyrrolidone, after 80 DEG C of constant temperature stir 30min, polyvinyl alcohol is dissolved completely, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in oil phase storage tank keep 0.1MPa, open the second variable valve, oil phase fluid is entered in polymerization reaction kettle by nozzle dispersion and forms O/W suspension in aqueous phase, constant temperature 80 DEG C reaction 3h;
(4) be cooled to room temperature, filtered polymeric microballon, by water, acetone, washing with alcohol, to remove pore-creating agent, expanded polystyrene microballon can be obtained.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (3)
1. a preparation method for polymer bead, the aperture of described polymer bead is adjustable, said method comprising the steps of:
(1) hydrophobicity vinyl monomer is mixed with oil-soluble initiator, fully stir, form homodisperse oil phase fluid; Described mixing and being stirred in oil phase storage tank completes; Described oil-soluble initiator is benzoyl peroxide;
(2) in stirring-type polymerization reaction kettle, add stablizer and water, dispersed with stirring forms uniform aqueous phase solution;
(3) add suitable pressure, described oil phase fluid is entered in described aqueous phase solution by nozzle dispersion and forms uniform O/W type suspension;
(4) constant temperature polyreaction, can obtain the polymer bead of uniform particle diameter; The temperature of described polyreaction is 70 ~ 90 DEG C;
Described hydrophobicity vinyl monomer is made up of one or more hydrophobicity vinyl monomer; Described hydrophobicity vinyl monomer is vinylbenzene, divinylbenzene, methyl methacrylate, methyl acrylate, vinyl acetate, glycidyl methacrylate or derivatives thereof, and described stablizer is the mixture of polyvinyl alcohol, polyvinylpyrrolidone, Mierocrystalline cellulose and HPMC;
Preparation method's special purpose device of described polymer bead, described device is jet flow suspension polymerization device, described jet flow suspension polymerization device comprises polymerization reaction kettle, oil phase storage tank and nozzle, oil phase storage tank upper end first variable valve is connected with nitrogengas cylinder, and is connected through the nozzle of the second variable valve with polymerization reaction kettle upper end; Oil phase storage tank upper end is provided with tensimeter and motor, and driven by motor agitator rotates.
2. the method for claim 1, is characterized in that, the temperature of described polyreaction is 80 DEG C.
3. method as claimed in claim 1 or 2, is characterized in that, comprise the following steps:
(1) jet flow suspension polymerization device is prepared:
Described jet flow suspension polymerization device comprises polymerization reaction kettle, oil phase storage tank and nozzle, and oil phase storage tank upper end first variable valve is connected with nitrogengas cylinder, and is connected through the nozzle of the second variable valve with polymerization reaction kettle upper end; Oil phase storage tank upper end is provided with tensimeter and motor, and driven by motor agitator rotates;
(2) hydrophobicity vinyl monomer is mixed with oil-soluble initiator, fully stir, in oil phase storage tank, form homodisperse oil phase fluid;
(3) in stirring-type polymerization reaction kettle, add stablizer and water, dispersed with stirring forms uniform aqueous phase solution;
(4) add suitable pressure, the oil phase fluid in oil phase storage tank is entered in aqueous phase by nozzle dispersion and forms uniform O/W type suspension;
(5) constant temperature polyreaction, can obtain the polymer bead of uniform particle diameter.
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| CN102731705B (en) * | 2012-07-18 | 2014-05-07 | 常州嘉众新材料科技有限公司 | Preparation method of high-purity spherical full-hole polystyrene-based particles |
| CN105852195A (en) * | 2015-01-22 | 2016-08-17 | 于杰 | Functional tobacco shreds |
| CN110358014A (en) * | 2019-05-28 | 2019-10-22 | 苏州知益微球科技有限公司 | A kind of preparation method of polymer beads |
| CN110498879A (en) * | 2019-09-06 | 2019-11-26 | 苏州知益微球科技有限公司 | A kind of preparation method of black polymer microballoon |
| CN110498878A (en) * | 2019-09-06 | 2019-11-26 | 无锡迈科为生物科技有限公司 | A kind of preparation method of fluorescent microsphere |
| CN110511309A (en) * | 2019-09-06 | 2019-11-29 | 无锡迈科为生物科技有限公司 | A kind of preparation method of magnetic macromolecular microsphere |
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| CN2630247Y (en) * | 2003-06-24 | 2004-08-04 | 中国科学院过程工程研究所 | Suspension polymerization apparatus |
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| CN1640921A (en) * | 2004-01-06 | 2005-07-20 | 中国科学院过程工程研究所 | Method for preparing super paramagnetic high polymer homogeneous microball |
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| CN2693338Y (en) * | 2003-12-22 | 2005-04-20 | 中国科学院过程工程研究所 | Jet flow type suspension polymerization reacting apparatus |
| CN1640921A (en) * | 2004-01-06 | 2005-07-20 | 中国科学院过程工程研究所 | Method for preparing super paramagnetic high polymer homogeneous microball |
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